CN106944112A - One kind is used for high acid value waste oil fat pre-esterification solid acid catalyst - Google Patents
One kind is used for high acid value waste oil fat pre-esterification solid acid catalyst Download PDFInfo
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- CN106944112A CN106944112A CN201710157289.1A CN201710157289A CN106944112A CN 106944112 A CN106944112 A CN 106944112A CN 201710157289 A CN201710157289 A CN 201710157289A CN 106944112 A CN106944112 A CN 106944112A
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- Prior art keywords
- solid acid
- acid catalyst
- acid value
- esterification
- waste oil
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 239000002253 acid Substances 0.000 title claims abstract description 69
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 62
- 230000032050 esterification Effects 0.000 title claims abstract description 58
- 239000011973 solid acid Substances 0.000 title claims abstract description 58
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 23
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000004615 ingredient Substances 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 239000003921 oil Substances 0.000 claims description 37
- 238000001354 calcination Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000004519 grease Substances 0.000 claims description 18
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 11
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 11
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 5
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 238000010924 continuous production Methods 0.000 claims description 4
- 238000009938 salting Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 239000002440 industrial waste Substances 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims 1
- 235000019837 monoammonium phosphate Nutrition 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 25
- 239000003225 biodiesel Substances 0.000 description 9
- 238000009740 moulding (composite fabrication) Methods 0.000 description 8
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- -1 cobaltous sulfates Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- RFYUQSQGLHNNOY-UHFFFAOYSA-N cobalt;sulfuric acid Chemical compound [Co].OS(O)(=O)=O RFYUQSQGLHNNOY-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012374 esterification agent Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical class O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the synthesis of solid acid catalyst and application, it is specifically related to a kind of for solid acid catalyst of high acid value waste oil fat pre-esterification and preparation method thereof and application method, the solid acid catalyst includes alumina support and the metal component and nonmetallic ingredient that are carried on alumina catalyst support, and the chemical formula of the solid acid catalyst is M Mo P/Al2O3, wherein M can be Co, Ni, Sn, one or more of in Sb.The preparation method of the solid acid catalyst is：Aluminum oxide is placed in impregnation drying in the mixed solution prepared twice to calcine, solid acid catalyst is made.The solid acid catalyst does not corrode to consersion unit, and is easy to separate with reaction product.Utilized after catalyst use through activation is repeatable, catalytic activity is without obvious reduction after 10 reuses.Continuous to evaluate 120 hours, catalytic activity is good, the prospects for commercial application that especially pre-esterification to high acid value waste oil fat has had.
Description
Technical field
The invention belongs to novel environment friendly catalyst technical field, and in particular to one kind is used for high acid value waste oil fat pre-esterification
Solid acid catalyst and preparation method thereof and application method.
Background technology
The excessive exploitation of petroleum resources cause holding at high price and obtaining increasingly the problems such as worsening shortages for it
Many concerns.Find the heat subject that new fungible energy source has become the world today.Biodiesel is sustainable as one kind
Clean energy resource, with excellent environmental protection characteristic energy, the discharge capacity of sulfur dioxide and sulfide is low in combustion product, with can be again
Raw, economy and good security performance, are a kind of new green environment protection energy, but the preparation of biodiesel but has raw material
High expensive, the problems such as production liquid acid catalyst used pollutes seriously corroded.Therefore, reduce cost of material and develop Novel ring
It is the important channel solved the problems, such as to protect catalyst.
High acid value waste oil fat ester has higher initial acid value, if directly with its exchange system for biodiesel, can
Cause base catalyst poisoning and deactivation because acid value is too high.Therefore, before using high acid value waste oil fat, raw material need to be carried out pre-
Esterification, the acid value of the waste grease of high acid value is reduced, base catalyst preparing biodiesel by ester exchange is then used again.If
The acid value reducing effect of pre-esterification is not up to standard, then can directly affect biodiesel yield in subsequent reactions, therefore high acid value is discarded
Pre-esterification conversion ratio is higher during preparing biodiesel from lipid, and it is lower that acid value is reduced, and biodiesel yield is bigger.On the market
Pre-esterification catalyst used is liquid acid catalyst, such as concentrated sulfuric acid, p-methyl benzenesulfonic acid etc. mostly, there is relative at a lower temperature
After higher catalytic activity, pre-esterification high conversion rate, but equipment corrosion are serious, and reaction terminates, need to add in reaction solution
Substantial amounts of caustic soda is neutralized, and generation is a large amount of liquid and waste slag produced, while being not readily separated there is also catalyst and stock Product and work
The shortcomings of continuous production is difficult in skill.
CN104004596A is disclosed using ferric sulfate as pre-esterification catalyst, solves the etching problem to equipment,
But catalyst separates needs from product and passes through the subsequent technique such as standing, extraction, stirring, filtering, dry, operating process complexity.
CN101016474A discloses a kind of method of solid low-kappa number high-acid value grease, the soybean oil after this solid acid treatment and
The grease that reconciles of oleic acid carries out the yield more than 90% of biodiesel after ester exchange with methanol, but handles waste grease（Acid value
20.1）Biodiesel yield there was only 84%, pre-esterification effect of its catalyst in the waste grease more containing impurity is paid no attention to
Think.
Present invention aims at the solid acid catalyst for providing a kind of high acid value waste oil fat pre-esterification and its preparation side
Method and application method, the solid acid catalyst reaction condition is gentle, easily separated and recovered with product and utilization is repeated after activation,
The waste grease that acid value is 140-260mg/g can be handled, is reused 10 times, acid value can drop to 0.5-5；Continuous pre-esterification
120h, catalyst remains to keep higher catalytic activity.Present invention also offers two kinds of high acid value waste oil fat pre-esterification
The application method of solid acid catalyst, one kind is used in the production of intermittent stirring formula；It is another to be used in tower continuous production.
The content of the invention
In order to solve the above-mentioned technical problem, the application provides a kind of solid acid catalysis of high acid value waste oil fat pre-esterification
Agent and preparation method thereof and application method.
One kind is used for high acid value waste oil fat pre-esterification solid acid catalyst, and the solid acid catalyst includes alumina support
And metal component and nonmetallic ingredient on alumina catalyst support are carried on, the chemical formula of the solid acid catalyst is M-Mo-P/
Al2O3。
It is preferred that, M is Co, Ni, Sn, the one or more in Sb in solid acid catalyst composition.
A kind of preparation method for high acid value waste oil fat pre-esterification solid acid catalyst, comprises the following steps：
（a）Molybdate and diammonium hydrogen phosphate wiring solution-forming soluble in water is standby；
（b）By step（a）In obtained solution be uniformly added dropwise to γ-Al2O3On, and uniform stirring 0.5-2 h, by gained solid
4-12h is dried at 90-130 DEG C, after calcining 1-6h at 400-800 DEG C, Mo-P/Al is obtained2O3；
（c）M salt is soluble in water, and to be made into M salting liquids standby；
（d）By step（c）In obtained M salting liquids, be added drop-wise to step（b）Obtained Mo-P/Al2O3On, be well mixed after
80-120 DEG C of dry 4-12h, 500-900 DEG C of calcining 1-6h, obtains pre-esterification solid acid catalyst M-Mo-P/Al2O3。
It is preferred that, molybdate, diammonium hydrogen phosphate, aluminum oxide, M salt, the mol ratio of water are 0.01-0.1: 0.01-0.1:
0.05-0.2: 0.01-0.1: 1.1-11；The step（a）The mol ratio of middle molybdate and water is 0.01-0.1：1-10；Institute
State step（c）The mol ratio of middle M salt and water is 0.01-0.1：0.1-1.
It is preferred that, step（a）Described in molybdate be ammonium heptamolybdate, potassium molybdate, sodium molybdate one or more therein.
It is preferred that, step（a）Described in diammonium hydrogen phosphate can be by sodium dihydrogen phosphate or disodium hydrogen phosphate or di(2-ethylhexyl)phosphate
Hydrogen ammonium or phosphoric acid are replaced.
It is preferred that, step（c）Described in M salt be cobaltous sulfate, nickel sulfate, stannous chloride, antimony acetate, cobalt nitrate in one
Plant or a variety of.
It is preferred that, step（b）Described in drying temperature be 110-120 DEG C, drying time is 8-10h, and calcining heat is
500-700 DEG C, calcination time is 2-4h；Step（d）Described in drying temperature be 100-110 DEG C, drying time is 8-10h,
Calcining heat is 500-700 DEG C, and calcination time is 4-5h.
A kind of application method for high acid value waste oil fat pre-esterification solid acid catalyst, including following two users
Method：
（a）Batch type is produced：It is 0.4- by weight by high acid value waste oil fat, methanol and pre-esterification solid acid catalyst
1.8:1:0.02-0.4 ratio is added in reactor, opens reaction unit, 1- is reacted under the conditions of being warming up to 70-150 DEG C
12h, reaction is cooled to after room temperature, catalyst filtration after terminating to be utilized through overactivation is repeatable, and filtrate decompression steams not anti-
The methanol answered, surveys product acid value, calculates pre-esterification rate；
（b）Tower continuous production：Parts by weight are loaded in the reactor, by 0.4- for 0.02-0.4 parts of solid acid catalyst
1.8 parts by weight high acid value waste oils and 1 parts by weight Methanol are passed through in reactor respectively through measuring pump, are 70-150 DEG C in temperature
Under the conditions of react 1-120h, reaction takes product to survey acid value after terminating, calculate pre-esterification rate
It is preferred that, industrial waste grease of the initial acid value of waste grease in 140-260mgKOH/g.
The present invention is using SN/T 0803.8-1999《Import and export oil plant free fatty, the acid value method of inspection》Survey before reaction
Acid value afterwards, calculates pre-esterification rate.
A kind of high acid value waste oil fat pre-esterification solid acid catalyst of the present invention, to high acid value waste oil fat
（140-260mg KOH/g）Pre-esterification there is acid value after good catalytic performance, pre-esterification to can reach 0.5-5 mg KOH/g；Urge
Agent does not have corrosivity to consersion unit, it is easy to separated with reaction product, is environmentally friendly solid acid catalyst；Catalyst makes
Utilized after through activation is repeatable, catalytic activity is without obvious reduction after 10 reuses.Successive reaction 120 hours, catalysis is lived
It is functional, for handling the prospects for commercial application that the waste grease of high acid value has had.
Brief description of the drawings
The technique that Fig. 1 reacts for a kind of high acid value waste oil fat pre-esterification solid acid catalyst of the present invention in batch tank
Flow chart；
Fig. 2 is a kind of high acid value waste oil fat pre-esterification solid acid catalyst of the invention in tower continuous reaction apparatus sketch；
Fig. 3 reuses evaluation result figure for a kind of high acid value waste oil fat pre-esterification solid acid catalyst of the present invention；
Fig. 4 is a kind of evaluation result of high acid value waste oil fat pre-esterification solid acid catalyst continuous esterification of the present invention
Figure；
In figure, 1, reactor；2nd, preheater；3rd, nitrogen cylinder；4th, methanol tank；5th, syringe pump；6th, accumulator tank；7th, water tank.
Embodiment
Embodiment 1
By 2.49g ammonium molybdates, 2.66g diammonium hydrogen phosphates, 38.20g water wiring solution-formings uniformly drip to 15.88g aluminum oxide after standing
（γ-Al2O3）On, 1 h, 100 DEG C of dry 8h are stirred, 500 DEG C of calcining 1h obtain Mo-P/Al2O3.By the water sulfuric acid of 2.63g six
Nickel, 0.29g antimony acetates, 7.91g water is configured to solution, is added drop-wise to Mo-P/Al2O3In, 80 DEG C of dry 12h, 500 DEG C of calcining 6h,
Obtain pre-esterification solid acid catalyst Ni-Sb-Mo-P/Al2O3-1。
High acid value waste oil fat, methanol and pre-esterification solid acid catalyst are separately added into reactor, initial acid value is surveyed,
80 DEG C of reactions, the mass ratio of wherein methanol and grease is 1.5：1, the addition quality of catalyst is the 30% of grease, reacts 12h
Afterwards, room temperature is cooled to, catalyst is filtered to isolate, filtrate decompression is distilled out into methanol, acid value is surveyed, pre-esterification rate is calculated.Technique
Flow chart is shown in Fig. 1, the results are shown in Table 1.
Embodiment 2
By 3.53g ammonium molybdates, 1.66g diammonium hydrogen phosphates, 20.42g water wiring solution-forming uniformly drips to 10.25g aluminum oxide after standing
（γ-Al2O3）On, 0.5 h, 110 DEG C of dry 8h are stirred, 500 DEG C of calcining 2h obtain Mo-P/Al2O3.By 5.63g sulfuric acid
Cobalt, 0.45g stannous chlorides, 5.23g water is configured to solution, drips to Mo-P/Al2O3On, 110 DEG C of dry 10h, 500 DEG C of calcining 5h,
Obtain pre-esterification solid acid catalyst Co-Sb-Mo-P/Al2O3-1。
High acid value waste oil fat, methanol and pre-esterification solid acid catalyst are separately added into reactor, initial acid value is surveyed,
100 DEG C of reactions, the mass ratio of wherein methanol and grease is 1.5：1, the addition quality of catalyst is the 20% of grease.React 12h
Afterwards, room temperature is cooled to, catalyst is filtered to isolate, filtrate decompression is distilled out into methanol, 200 DEG C of -290 DEG C of cuts are collected, acid is surveyed
Valency, calculates pre-esterification rate.Process chart is shown in Fig. 1, the results are shown in Table 1.
Embodiment 3
By 2.49g ammonium molybdates, 1.96g phosphoric acid, 38.20g water wiring solution-formings uniformly drip to 15.88g aluminum oxide after standing（γ-
Al2O3）On, 1h, 120 DEG C of dry 10h are stirred, 700 DEG C of calcining 4h obtain Mo-P/Al2O3.By the water nickel nitrates of 5.82g six,
0.29g antimony acetates, 7.91g water is configured to solution, is added drop-wise to Mo-P/Al2O3On, 100 DEG C of dry 8h, 700 DEG C of calcining 4h are obtained
Pre-esterification solid acid catalyst Ni-Sb-Mo-P/Al2O3-2。
The application method be the same as Example 1 of catalyst, the results are shown in Table 1.
Embodiment 4
By 3.53g ammonium molybdates, 1.25g phosphoric acid, 20.42g water wiring solution-formings uniformly drip to 10.25g aluminum oxide after standing（γ-
Al2O3）On, 0.5 h, 100 DEG C of dry 8h are stirred, 400 DEG C of calcining 2h obtain Mo-P/Al2O3.By 5.91g cobalt nitrates,
0.45g stannous chlorides, 5.23g water is configured to solution, is added drop-wise to Mo-P/Al2O3In, 100 DEG C of dry 10h, 800 DEG C of calcining 3h,
Obtain pre-esterification solid acid catalyst Co-Sb-Mo-P/Al2O3-2。
The application method be the same as Example 2 of catalyst, the results are shown in Table 1.
Embodiment 5
By 2.49g ammonium molybdates, 2.66g diammonium hydrogen phosphates, 38.20g water wiring solution-formings uniformly drip to 15.88g aluminum oxide after standing
（γ-Al2O3）On, 1 h, 130 DEG C of dry 8h are stirred, 800 DEG C of calcining 1h obtain Mo-P/Al2O3.By the water sulfuric acid of 2.63g six
Nickel, 7.91g water is configured to solution, is added drop-wise in Mo-P/Al2O3,80 DEG C of dry 12h, 500 DEG C of calcining 6h, obtains pre-esterification
Solid acid catalyst Ni-Mo-P/Al2O3.
The application method be the same as Example 1 of catalyst, the results are shown in Table 1.
Embodiment 6
By 3.53g ammonium molybdates, 1.66g diammonium hydrogen phosphates, 20.42g water wiring solution-formings uniformly drip to 10.25g aluminum oxide after standing
（γ-Al2O3）On, 2 h, 90 DEG C of dry 12h are stirred, 500 DEG C of calcining 6h obtain Mo-P/Al2O3.By 5.63g cobaltous sulfates,
5.23g water is configured to solution, drips on Mo-P/Al2O3,100 DEG C of dry 4h, 900 DEG C of calcining 3h, obtains pre-esterification solid acid
Catalyst Co-Mo-P/Al2O3。
The application method be the same as Example 2 of catalyst, the results are shown in Table 1
Embodiment 7
By 3.53g ammonium molybdates, 1.66g diammonium hydrogen phosphates, 20.42g water wiring solution-formings uniformly drip to 10.25g aluminum oxide after standing
（γ-Al2O3）On, 2 h, 90 DEG C of dry 12h are stirred, 500 DEG C of calcining 6h obtain Mo-P/Al2O3.By 1.20g cobaltous sulfates,
1.33g nickel sulfate hexahydrates, 0.12g antimony acetates, 1.55g cobalt nitrates, 0.24g stannous chlorides, 5.23g water is configured to solution, drips to
On Mo-P/Al2O3,100 DEG C of dry 4h, 900 DEG C of calcining 3h obtain pre-esterification solid acid catalyst Co-Mo-P/Al2O3。
The application method be the same as Example 1 of catalyst, the results are shown in Table 1.
Embodiment 8
The preparation method be the same as Example 1 of catalyst.
High acid value waste oil fat, methanol and pre-esterification solid acid catalyst are separately added into reactor, initial acid value is surveyed,
90 DEG C of reactions, the mass ratio of wherein methanol and grease is 1.5：1, the addition quality of catalyst is the 20% of grease.React 12h
Afterwards, room temperature is cooled to, catalyst is filtered to isolate, it is stand-by after activation, 200 DEG C of -290 DEG C of cuts are collected into filtrate decompression distillation,
Acid value is surveyed, pre-esterification rate is calculated.The catalyst isolated, suction filtration is rinsed with absolute methanol, and above-mentioned reaction is repeated after drying.
Reuse 10 times altogether, per the complete record acid value of secondary response, calculate pre-esterification rate.Process chart is shown in Fig. 1, the results are shown in Table 2 Hes
Fig. 3.
Embodiment 9
The preparation method be the same as Example 1 of catalyst.
By the filling of 1.5g solid acid catalysts in the reactor, 150 DEG C of temperature of reactor is set.By high acid value waste oil fat
Reactor is pumped into 5mL/h speed, 50mL/h methanol passes through preheater（120℃）Into reactor, the h of mass space velocity 1.5-1,
120h is reacted, every 12 h takes product to survey acid value, calculates pre-esterification rate, and reaction unit sketch is shown in Fig. 2, the results are shown in Table 3 and Fig. 4.
By to scheme the waste grease with catalyst treatment acid value described herein it can be seen from table as 140-260, repeating
Using 10 times, the catalytic effect of catalyst is basically unchanged；Continuous pre-esterification 120h, the catalysis that catalyst remains to keep higher is lived
Property.
The application uses SN/T 0803.8-1999《Import and export oil plant free fatty, the acid value method of inspection》Survey before reaction
Acid value afterwards, calculates pre-esterification rate.
Technical solution of the present invention is not limited to following all embodiments, also including between each embodiment
Any combination；Invention prepares high activity by carried metal element by carrier of aluminum oxide and can be used for the pre- ester of peracid value waste oil
Change reaction, pre-esterification rate more than 95%, with higher catalytic activity；Catalyst is corrosion-free to equipment, environmental protection, is green
Environment protection solid acid catalyst.
Claims (10)
1. one kind is used for high acid value waste oil fat pre-esterification solid acid catalyst, it is characterised in that the solid acid catalyst is included
Alumina support and the metal component and nonmetallic ingredient being carried on alumina catalyst support, the chemical formula of the solid acid catalyst
For M-Mo-P/Al2O3。
2. it is according to claim 1 a kind of for high acid value waste oil fat pre-esterification solid acid catalyst, it is characterised in that
M is Co in solid acid catalyst composition, Ni, Sn, the one or more in Sb.
3. a kind of preparation method for high acid value waste oil fat pre-esterification solid acid catalyst according to claim 1,
It is characterised in that it includes following steps：
（a）Molybdate and diammonium hydrogen phosphate wiring solution-forming soluble in water is standby；
（b）By step（a）In obtained solution be uniformly added dropwise to γ-Al2O3On, and uniform stirring 0.5-2 h, by gained solid
4-12h is dried at 90-130 DEG C, after calcining 1-6h at 400-800 DEG C, Mo-P/Al is obtained2O3；
（c）M salt is soluble in water, and to be made into M salting liquids standby；
（d）By step（c）In obtained M salting liquids, be added drop-wise to step（b）Obtained Mo-P/Al2O3On, be well mixed after
80-120 DEG C of dry 4-12h, 500-900 DEG C of calcining 1-6h, obtains pre-esterification solid acid catalyst M-Mo-P/Al2O3。
4. a kind of preparation method for high acid value waste oil fat pre-esterification solid acid catalyst according to claim 3,
Characterized in that, the mol ratio of the molybdate, diammonium hydrogen phosphate, aluminum oxide, M salt, water is 0.01-0.1: 0.01-0.1:
0.05-0.2: 0.01-0.1: 1.1-11；The step（a）The mol ratio of middle molybdate and water is 0.01-0.1：1-10；Institute
State step（c）The mol ratio of middle M salt and water is 0.01-0.1：0.1-1.
5. a kind of preparation method for high acid value waste oil fat pre-esterification solid acid catalyst according to claim 3,
Characterized in that, the molybdate described in step a is ammonium heptamolybdate, potassium molybdate, sodium molybdate one or more therein.
6. a kind of preparation method for high acid value waste oil fat pre-esterification solid acid catalyst according to claim 3,
Characterized in that, step（a）Described in diammonium hydrogen phosphate can be by sodium dihydrogen phosphate or disodium hydrogen phosphate or ammonium dihydrogen phosphate
Or phosphoric acid is replaced.
7. a kind of preparation method for high acid value waste oil fat pre-esterification solid acid catalyst according to claim 3,
Characterized in that, step（c）Described in M salt be cobaltous sulfate, nickel sulfate, stannous chloride, antimony acetate, cobalt nitrate in one kind or
It is a variety of.
8. a kind of preparation method of high acid value waste oil fat pre-esterification solid acid catalyst according to claim 3, it is special
Levy and be, step（b）Described in drying temperature be 110-120 DEG C, drying time is 8-10h, and calcining heat is 500-700
DEG C, calcination time is 2-4h；Step（d）Described in drying temperature be 100-110 DEG C, drying time is 8-10h, calcining heat
For 500-700 DEG C, calcination time is 4-5h.
9. a kind of application method for high acid value waste oil fat pre-esterification solid acid catalyst as claimed in claim 1, its
It is characterised by, including following two application methods：
（a）Batch type is produced：It is 0.4- by weight by high acid value waste oil fat, methanol and pre-esterification solid acid catalyst
1.8:1:0.02-0.4 ratio is added in reactor, opens reaction unit, 1- is reacted under the conditions of being warming up to 70-150 DEG C
12h, reaction is cooled to after room temperature, catalyst filtration after terminating to be utilized through overactivation is repeatable, and filtrate decompression steams not anti-
The methanol answered, surveys product acid value, calculates pre-esterification rate；
（b）Tower continuous production：Parts by weight are loaded in the reactor, by 0.4- for 0.02-0.4 parts of solid acid catalyst
1.8 parts by weight high acid value waste oils and 1 parts by weight Methanol are passed through in reactor respectively through measuring pump, are 70-150 DEG C in temperature
Under the conditions of react 1-120h, reaction takes product to survey acid value after terminating, calculate pre-esterification rate.
10. a kind of application method that solid acid catalyst is esterified for high acid value waste oil fat as claimed in claim 9, it is special
Levy and be, industrial waste grease of the initial acid value of waste grease in 140-260mgKOH/g.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016474A (en) * | 2007-02-28 | 2007-08-15 | 南京财经大学 | Method of preparing biological diesel oil from high acid value grease by solid acid pretreatment |
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| CN101016474A (en) * | 2007-02-28 | 2007-08-15 | 南京财经大学 | Method of preparing biological diesel oil from high acid value grease by solid acid pretreatment |
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| Title |
|---|
| 林凌等: "免预硫化的加氢脱硫MoNiP/Al2O3 催化剂的制备和表征", 《催化学报》 * |
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